COORDINATION CHEMISTRY

Coordination Chemistry
Coordination numbers and geometries
In this unity, it is given an overview of the coordination numbers and
geometries found within d-block metal compounds. Some considerations

• Most examples in this section involve mononuclear complexes, and in

complexes with more than one metal centre, structural features are often
conveniently described in terms of individual metal centres;

• Although coordination environments are often described in terms of regular

geometries, in practice they are often distorted, for example as a consequence
of steric effects;

• Detailed discussion of a particular geometry usually involves bond lengths and

angles determined in the solid state and these may be affected by crystal
packing forces;

• where the energy difference between different possible structures is small (e.g.
for 5- and 8-coordinate complexes), fluxional behaviour in solution may be
observed
 Coordination Chemistry
It is difficult to provide generalizations about the trends in coordination number
within the d-block. However, it is useful to bear the following points in mind:

1. Sterically demanding ligands favour low coordination numbers at metal centres;

2. High coordination numbers are most likely to be attained with small ligands
and large metal ions;
3. The size of a metal ion decreases as the formal charge increases, e.g.
r(Fe3+)<r(Fe2+); 

4. Low coordination numbers will be favoured by metals in high oxidation states
with π-bonding ligands.
 Coordination Chemistry

Alfred Werner – Premio Nobel 1913

the term complex means

a central metal atom or
ion surrounded by a set
of ligands. A ligand is an
ion or molecule that can
have an independent
existence.
Reactividad Ag+ Conductiv.

CoCl3 . 6NH3 amarillo exceso Ag+ 3 moles AgCl 4 iones

CoCl3 . 5NH3 púrpura exceso Ag+ 2 moles AgCl 3 iones

CoCl3 . 4NH3 verde y violeta exceso Ag+ 1 mol AgCl 2 iones

CoCl3 . 3NH3 dos compuestos exceso Ag+ 0 moles AgCl neutro

 Coordination Chemistry

[Co(NH3)6]Cl3 [Co(NH3)5Cl]Cl2 [Co(NH3)4Cl2]Cl

2+ +
3+

Conclusiones de Werner

1. The metal is in a certain oxidation staten (primary valence)

2. The complex has a fix coordination number (secondary valence)

3. Ligands are bounded to the metal centre through a similar covalent bond
 Coordination Chemistry

n+/- Charge of the complex

ligands
X+/-
n

Metal ion counterion

L
The central atom ion is surrounded by ligands
L L

The ligand donates two electrons to the d L L

metal orbitals (coordinative donating bond)
L
 Coordination Chemistry
Coordination numbers in the solid state
A general word of caution: molecular formulae can be
misleading in terms of coordination number

α-PdCl2 is polymeric

A further ambiguity arises when the bonding mode of a ligand

can be described in more than one way:

[η 5 − C5H5]− ligand
occupying one or five sites
in the coordination sphere

[(η 5 − C5H5)2TiCl2]
 Coordination Chemistry
The language of coordination chemistry
In an inner-sphere complex, the ligands are attached directly to
a central metal ion; outer-sphere complexes occur where cation
and anion associate in solution.

In inner-sphere complexes, the ligands form the primary

coordination sphere of the complex and their number is called
the coordination number of the central metal atom

A wide range of
coordination numbers
can be achieved up to 12

[Co(NH3)6]Cl3
 Coordination Chemistry
Representative ligands
Polydentate ligands can form chelates; a bidentate ligand with a
small bite angle can result in distortions from standard
structures
 Coordination Chemistry
Representative ligands
 Coordination Chemistry
Representative ligands
 Coordination Chemistry
Representative ligands
 Coordination Chemistry
Representative ligands
 Coordination Chemistry
Denticity of a ligand
Denticity refers to the number of donor groups in a single ligand that
bind to a central atom in a coordination complex.

Some of these ligands have only a single donor pair of electrons and
will have only one point of attachment to the metal: such ligands are
classified as monodentate. Ligands that have more than one point
of attachment are classified as polydentate.

Ambidentate ligands have more than

one different potential donor atom

Nitrito-!κO ligand Nitrito-!κN ligand

 Coordination Chemistry
Chelate ligands
Polydentate ligands can produce a chelate, a complex in which a
ligand forms a ring that includes the metal atom

Ethylenediamine ligand (en)

[Co(edta)]-

The degree of strain in a chelating

ligand is often expressed in terms of
the bite angle, the L-M-L angle in
the chelate ring
 Coordination Chemistry
Most representative ligands

H 2N NH2
ethilendiamine (en) N N N
!!
N
!!
!! !!

2,2’-bypyridine (bpy) 1,10-phenantroline (phen)

Ph2P !!
PPh 2
!!

1,2-bis-diphenylphosphine ethane
(dppe)

O O
O
N
H 3C - -
O O N N
O
acetate (Ac) 2,2’:6,2”-terpyridine (tpy)
oxalate (ox)
 Coordination Chemistry
Most representative ligands

CO
Group 14 C O carbon monoxide

NH3 PPh3
Group 15 :
ammonia triphenylphosphine

:
:
:

: H2O SR2
Group 16
water thioether
 Coordination Chemistry
Most representative ligands - charged ligands
Group 14 C N: CN- Ph-
cyanide phenyl

Group 15 N O: NO- N C S: NCS-

nitro isocyanide

Group 16 OH- SCN-

O H S C N:
hydroxo thiocyanate

Group 17 X halo H hydride

These ligands bound to the metal centre through sigma bonds

 Coordination Chemistry
El modelo de enlace de Lewis. Sidgwick

Most representative ligands - σ bonds

“Lewis base"
Example: [Co(NH3)6]3+

NH3 3+

:
6
H3N: :NH3
:

N + Co3+
H H3N: : NH3
H
H

:
NH3

“Lewis acid”
 Coordination Chemistry
Most representative ligands - π donor bond

H2C CH2 RC CR

-
CH2 Zeise’s Salt
Cl
K+ Cl Pt First organometallic compound
Cl CH2

[PtCl3(η2-C2H4)]-

η 2-ethilene means that the C2H4 bond to

the metal through two carbon atoms
 Coordination Chemistry
Constitution and geometry
The number of ligands in a complex depends on the size of the metal
atom, the identity of the ligands, and the electronic interactions.

Three factors govern the coordination number of a complex:

1. The size of the central atom or ion.

2. The steric interactions between the ligands.

3. Electronic interactions between the central atom or ion and
the ligands.

M-Ln
n = number of ligands
 Coordination Chemistry
Low coordination numbers - Two coordinate complexes

Two-coordinate complexes are found for Cu and Ag; these complexes

often accommodate more ligands if they are available.

Examples of coordination number 2 are uncommon, being generally

restricted to Cu(I), Ag(I), Au(I) and Hg(II)

Examples include
[CuCl 2 ] - , [Ag(NH 3 ) 2 ] + ,
[Au(CN)2]-, [R3P)AuCl,
[Au(PR3)2]+ (R = alkyl
or aryl, and Hg(CN)2

d10 ions!! [Au(PCy3)2]+

 Coordination Chemistry
Low coordination numbers - Two coordinate complexes

Two-coordinate complexes are found for Cu and Ag; these complexes

often accommodate more ligands if they are available.

Examples of coordination number 2 are uncommon, being generally

restricted to Cu(I), Ag(I), Au(I) and Hg(II)

Bulky ligands, e.g.

[N(SiR3)2]-, are
However, in the associated to low
solid state, Cu(I) coordination numbers
complexes︎ can
adopt 3-coordinate
environment through
cyano- or halide-
bridge formation

K[Cu(CN)2]
J. Organom. Chem. 689 (2004) 3904
 Coordination Chemistry
Low coordination numbers - Three coordinate complexes

Three-coordination is rare among metal complexes, but is found with

bulky ligands such as tricyclohexylphosphine, as in [Pt(PCy3)3]

examples involving d10 metal centres include:

Cu(I): [Cu(CN)3], [Cu(SPMe3)3]+

Ag(I): [AgTe7]3-, [Ag(PPh3)3]+
Au(I): [Au{PPh(C6H11)2}3]+
Hg(II): [HgI3]-, [Hg(SPh3)3]-
Pt(0): [Pt(PPh3)3], [Pt(PtBu2H)3]

[Fe{N(SiR3)2}3]
[Pt(PCy3)3]
 Coordination Chemistry
Low coordination numbers - Three coordinate complexes

Three-coordination is rare among metal complexes, but is found with

bulky ligands such as tricyclohexylphosphine, as in [Pt(PCy3)3]

examples involving d10 metal centres include:

The inclusion of
rigid chelate
ligand could lead
to three-coordinate
complexes

[Au(NHC)(PR2-PR2)]
 Coordination Chemistry
Intermediate coordination numbers

Complexes of metal ions with the intermediate coordination numbers

four, five, and six are the most important class of complex. They
include the vast majority of complexes that exist in solution and
almost all the biologically important complexes

Four Coordinate Complexes

Tetrahedral complexes

Tetrahedral complexes are

favoured over higher coordinate
complexes if the central atom is
small or the ligands large(such as
Cl, Br, and I) because then
ligand-ligand repulsions Tetrahedral complex (Td)

Four-coordinate s- and p-block complexes with no lone pair on the

central atom ([BeCl4]2-, [BF4]-, and [SnCl4]) are almost always tetrahedral
 Coordination Chemistry
Intermediate coordination numbers

Complexes of metal ions with the intermediate coordination numbers

four, five, and six are the most important class of complex. They
include the vast majority of complexes that exist in solution and
almost all the biologically important complexes

Four Coordinate Complexes

Tetrahedral complexes

Tetrahedral complexes are

common for oxoanions of
metal atoms on the left of
the d block in high
oxidation states, such as
[MoO4]2-

d3 and d4 ions are rarely with bulky ligands

 Coordination Chemistry
Intermediate coordination numbers

Complexes of metal ions with the intermediate coordination numbers

four, five, and six are the most important class of complex. They
include the vast majority of complexes that exist in solution and
almost all the biologically important complexes

Four Coordinate Complexes

Square Planar complexes

Square planar complexes are

rarer than tetrahedral, and Square-planar complex (D4h)
are often associated with d8
configurations of the elements
belonging to the 4d- and 5d-
series metals such as Rh+, Ir+,
Pd2+, Pt2+, and Au3+, which are
almost invariably square Cisplatin
planar PtCl2(NH3)2 [AuCl3(NHC)]
 Coordination Chemistry
Intermediate coordination numbers

Complexes of metal ions with the intermediate coordination numbers

four, five, and six are the most important class of complex. They
include the vast majority of complexes that exist in solution and
almost all the biologically important complexes

Four Coordinate Complexes

Square Planar complexes
Some exceptions of d7 ions are found. In
this case, the presence of strong π!
character ligands and bulky
countercations is crucial for the
stabilization of the square planar complex

Square-planar geometry PNP [Co(CN)4]

can also be forced by
Magnetic moment = 2.52 μB
complexation with a ligand
that contains a rigid ring
J. Am. Chem. Soc. 1984, 106, 4265-6
of four donor atoms
 Coordination Chemistry
Five Coordinate Complexes

The limiting structures for 5-coordination are the trigonal bipyramid

and square-based pyramid. Many structures lie between these two
extremes with small energy differences between them

Trigonal bipyramidal

Among simple 5-coordinate

complexes are trigonal
bipyramidal [CdCl5]3-, [HgCl5]3- and
[CuCl5]3- (d10) and a series of
square-based pyramidal oxo- or
nitrido-complexes in which the
[CoBrN(CH2CH2NMe2)3]2+ [Zn{N(CH2CH2NH2)3}Cl]+
oxo or nitrido ligand occupies
the axial site

A trigonal-bipyramidal shape minimizes ligand-ligand repulsions, but

steric constraints on ligands that can bond through more than one
site to a metal atom can favor a square-pyramidal structure.
 Coordination Chemistry
Five Coordinate Complexes

The limiting structures for 5-coordination are the trigonal bipyramid

and square-based pyramid. Many structures lie between these two
extremes with small energy differences between them

Square-based pyramidal

square-pyramidal five-
coordination is found among the
biologically important porphyrins,
where the ligand ring enforces a
square-planar structure and a
fifth ligand attaches above the
View of the active [Cu(bpy){NH(CH2CO2)2}]
plane
centre of myoglobin

the conformational constraints of the ligands may result in a

preference for a square-based pyramidal complex
 Coordination Chemistry
Five Coordinate Complexes

The limiting structures for 5-coordination are the trigonal bipyramid

and square-based pyramid. Many structures lie between these two
extremes with small energy differences between them

Square-based pyramidal

Square-based pyramidal oxo- or

nitrido-complexes in which the
oxo or nitrido ligand occupies
the axial site

WCl4(O)]- [TcCl4(N)]-

d0: [NbCl4(O)]-
d1: [V(acac)2O], [WCl4(O)]-, [TcCl4(N)]-, [TcBr4(N)]-
d2: [TcCl4(O)]-, [ReCl4(O)]-
 Coordination Chemistry
Six Coordinate Complexes

The vast majority of six coordinate compounds are mainly octahedral,

however, examples of trigonal prismatic coordination geometry are also
encountered
 Coordination Chemistry
Octahedral

This geometry is the most common among transition metal complexes.

The regular or nearly regular octahedral coordination sphere is found
for all electronic configurations from d0 to d10:

[TiF6]2- (d0), [Ti(OH2)6]3+ (d1), [V(OH2)6]3+ (d2), [Cr(OH2)6]3+ (d3), [Mn(OH2)6]3+

(d4), [Fe(OH2)6]3+ (d5), [Fe(OH2)6]2+ (d6), [Co(OH2)6]2+ (d7), [Ni(OH2)6]2+ (d8),
[Cu(NO2)6]4- (d9), [Zn(OH2)6]2+ (d10) → High spin complexes

Other octahedral low-spin complexes are also known:

[Mn(CN)6]3- (d4), [Fe(CN)6]3- (d5), [Co(CN)6]3- (d6) → High spin complexes

Nevertheless, octahedral complexes of d4 Equatorial

and d9 metal ions tend to be tetragonally Cu-O: 195 pm
distorted, i.e. they are elongated or Axial
squashed. This is an electronic effect called Cu-O: 238 pm
Jahn–Teller distortion
[Cu(OH2)6]2+
 Coordination Chemistry
Octahedral

This geometry is the most common among transition metal complexes.

The regular or nearly regular octahedral coordination sphere is found
for all electronic configurations from d0 to d10:
D4h

D2h D3d
Distortions of a regular octahedron: (a) and (b) tetragonal distortions, (c)
rhombic distortion, (d) trigonal distortion
 Coordination Chemistry
Octahedral

This geometry is the most common among transition metal complexes.

The regular or nearly regular octahedral coordination sphere is found
for all electronic configurations from d0 to d10:

A chelating ligand that permits only a small bite angle can distort an
octahedral complex into trigonal-prismatic geometry
 Coordination Chemistry
Trigonal Prismatic Coordination

There is a small group of d0 or d1 metal complexes in which the

metal centre is in a regular trigonal or distorted trigonal prismatic
environment.
Trigonal prismatic Octahedral

[Mn(acac)2(bpy)] [Mn(acac)2(phen)]

The solid state structures provide an example in which crystal packing

forces appear to dictate the difference in ligand arrangement
 Coordination Chemistry
Trigonal Prismatic Coordination

There is a small group of d0 or d1 metal complexes in which the

metal centre is in a regular trigonal or distorted trigonal prismatic
environment.

The complexes [ReMe6] (d1), [TaMe6]- (d0) and [ZrMe6]2- (d0) contain
regular trigonal prismatic (D3h) metal centres, while in [MoMe6] (d0),
[WMe 6 ] (d 0 ), [NbMe 6 ] - (d 0 ) and [TaPh 6 ] - (d 0 ) the coordination
environment is distorted trigonal prismatic (C3v)

[WMe6]
Science, 1996, vol. 271, p. 626]

The ligands are !σ-donors, with no π

! -donating or !π-accepting properties
 Coordination Chemistry
Trigonal Prismatic Coordination

There is a small group of d0 or d1 metal complexes in which the

metal centre is in a regular trigonal or distorted trigonal prismatic
environment.

The complexes [WL3], [TiL3]2-, [ZrL3]2- and [HfL3]2- also possess

trigonal prismatic structures.

Regular trigonal prismatic: !α = 0º

Distorted trigonal prismatic: !α = 3º and 15º

In [ML3]2- (M = Ti, Zr, Hf) the metal is in a -2

oxidation state. However, theoretical results for
L = [WL 3 ] indicate that negative charge is
transferred on to the ligands. In the extreme
case, the ligands can be formulated as L2-
and the metal as a d0 centre
 Coordination Chemistry
Seven Coordinate Complexes

High coordination numbers (︎7) are observed most frequently for ions
of the early second and third row d-block metals and for the
lanthanoids and actinoids, i.e. r must cation be relatively large

The coordination spheres defined by the donor atoms in idealized

7-coordinate structures
 Coordination Chemistry
Seven Coordinate Complexes

High coordination numbers (︎7) are observed most frequently for ions
of the early second and third row d-block metals and for the
lanthanoids and actinoids, i.e. r must cation be relatively large
 Coordination Chemistry
Seven Coordinate Complexes

High coordination numbers (≥7) are observed most frequently for ions
of the early second and third row d-block metals and for the
lanthanoids and actinoids, i.e. r must cation be relatively large

[TaCl4(PMe3)3] [ZrF7]3- [ScCl2(15-crown-5)]CuCl4

The capped octahedral structure of [TaCl4(PMe3)3] [Inorg. Chem., 1984, vol. 23, p.
4046], the capped trigonal prismatic [ZrF7]3- in the guanidinium salt [Koord. Khim.,
1985, vol. 11, p. 566], and the pentagonal bipyramidal cation in [ScCl2(15-
crown-5)]CuCl4 with the crown ether occupying the equatorial plane [Zh. Neorg. Khim.,
1992, vol. 37, p. 1822]
 Coordination Chemistry
Coordination Number 8

As the number of vertices in a polyhedron increases, so does the

number of possible structures.
 Coordination Chemistry
Coordination Number 8 - Cube

The best known 8-vertex polyhedron is the cube, but this is hardly
ever observed as an arrangement of donor atoms in complexes. The
few examples include the anions in the actinoid complexes Na3[PaF8],
Na3[UF8] and [Et4N]4[U(NCS-N)8].

Steric

hindrance
 Coordination Chemistry
Coordination Number 8 - Square Antiprism

Square antiprismatic coordination environments occur in [Zr(acac)4] (d0)

and in the anions in the salts Na3[TaF8] (d0), K2[ReF8] (d1) and
K2[H3NCH2CH2NH3][Nb(ox)4] (d1)

The square antiprismatic structure

of [Nb(ox)4]4- in the salt
K2[H3NCH2CH2NH3][Nb(ox)4]4H2O
 Coordination Chemistry
Coordination Number 8
Dodecahedron; triangulated decahedron
The energy difference between 8-coordinate structures tends to be
small (4 kcal) with the result that the preference between two structures
may be altered by crystal packing forces in two different salts

Dodecahedron Square Antiprism

Examples are seen in a range of salts of [Mo(CN)8]3-, [W(CN)8]3-,

[Mo(CN)8]4- or [W(CN)8]4- (Inorg. Chem. 2004, 43, 10, 3142-3150)
 Coordination Chemistry
Coordination Number 8
Dodecahedron; triangulated decahedron
The energy difference between 8-coordinate structures tends to
be small with the result that the preference between two structures
may be altered by crystal packing forces in two different salts

K+ CN
4- Na+
(NMe4)3Li H+
[Mn2+(H2O)]4 Depending Cs7Na
Mo
on the cation

[Mo(CN)8]4- (D2)
[(nBu)4N]3[Mo(CN)8] (This is an exception)

Image taken from: https://www.chemtube3d.com/mocn84/

(Provided by University of Liverpool)
 Coordination Chemistry
Coordination Number 8
Dodecahedron; triangulated decahedron
Further examples of dodecahedral complexes include [Y(OH2)8]3+ and a
number of complexes with bidentate ligands: [Mo(O2)4]2- (d0), [Ti(NO3)4]
(d0), [Cr(O2)4]3- (d1), [Mn(NO3)4]2- (d5) and [Fe(NO3)4]- (d5)

[Y(OH2)8]3+ (D2)

The dodecahedral ion [Y(OH2)8]3+ in the salt [Y(OH2)8]Cl3(15-crown-5)

 Coordination Chemistry
Coordination Number 8
Hexagonal bipyramid
The hexagonal bipyramid is a rare coordination environment, but may
be favored in complexes containing a hexadentate macrocyclic ligand

[CdBr2(18-crown-6)] with the macrocyclic ligand occupying the

equatorial plane of a hexagonal bipyramid
 Coordination Chemistry
Coordination Number 8
Bicapped trigonal prism
A bicapped trigonal prism is another option for 8-coordination, but is
only rarely observed, e.g. in [ZrF8]4- (d0) and [La(acac)3(OH2)2]⋅H2O (d0)

This shape has C2v symmetry

 Coordination Chemistry
Coordination Number 9
Tricapped trigonal prism
Nine-coordination is important in the structures of f-block elements;
their relatively large ions can act as host to a large number of
ligands. Simple examples of a nine-coordinate lanthanoid complexes
are [Nd(OH2)9]3, [Sc(OH2)9]3-, [Y(OH2)9]3- and [La(OH2)9]3-

Tricapped trigonal prism

The anions [ReH9]2- and [TcH9]2- (both d0) examples of 9-

coordinate species in which the metal centre is in a tricapped
trigonal prismatic environment
 Coordination Chemistry
Coordination Number 10 and above
Ten- and twelve-coordination are encountered in complexes of the f-block
M3+ ions. An example of a ten-coordinate complex is [Th(ox)4(OH2)2]4-, in
which each oxalate ion ligand provides two O donor atoms
 Coordination Chemistry
Coordination Number 10 and above
Complexes containing [BH4]- and related ligands are an exception, e.g. in
[Hf(BH4)4] and [Zr(MeBH3)4] the ligands are tridentate and the metal
centres are 12-coordinate

Cubeoctahedral geometry

The structure of [Hf(BH4)4] determined by neutron diffraction

at low temperature (Inorg. Chem., 1983, vol. 22, p. 1081)
 Coordination Chemistry
Polymetallic Complexes
Polymetallic complexes are complexes that contain more than one metal
atom. In some cases, the metal atoms are held together by bridging
ligands; in others there are direct metal-metal bonds

Bridging ligands

When no metal-metal bond is present, polymetallic complexes are

referred to as cage complexes
 Coordination Chemistry
Polymetallic Complexes
Polymetallic complexes are complexes that contain more than one metal
atom. In some cases, the metal atoms are held together by bridging
ligands; in others there are direct metal-metal bonds

Metal-metal bond

Hg

The term metal cluster is usually reserved for polymetallic

complexes in which there are direct metal-metal bonds that form
triangular or larger closed structures
 Coordination Chemistry
Class Work
 Coordination Chemistry
Class Work
 Coordination Chemistry
Class Work
Show that the trigonal bipyramid, square-based pyramid and square
antiprism belong to the point groups D3h, C4v and D4d, respectively

(a) In the solid state, Fe(CO)5 possesses a trigonal bipyramidal

structure. How many carbon environments are there? (b) Explain
why only one signal is observed in the 13C NMR spectrum of
solutions of Fe(CO)5 , even at low temperature
 Coordination Chemistry
Class Work
The following structures show bond angle data (determined by X-ray
diffraction) for some complexes with low coordination numbers. Comment
on these data, suggesting reasons for deviations from regular geometries.
 Coordination Chemistry
Nomenclature
1. Para escribir la fórmula de los complejos se coloca en primer lugar el símbolo del
átomo o ion central y a su derecha se van anotando primero los ligandos iónicos y
luego los neutros, siguiendo dentro de cada clase un orden alfabético (orden basado
en el símbolo de los átomos enlazados al ion central):
Hierro, agua y cianuro →[Fe(CN)5(H2O)]2-
Níquel, Cl y ClO4- → [NiCl3(ClO4)]2-
Cromo, F y O → [CrF4O]-
 Coordination Chemistry
Nomenclature
1. Para escribir la fórmula de los complejos se coloca en primer lugar el símbolo del
átomo o ion central y a su derecha se van anotando primero los ligandos iónicos y
luego los neutros, siguiendo dentro de cada clase un orden alfabético (orden basado
en el símbolo de los átomos enlazados al ion central):
2. Al nombrar dichos compuestos, primero se mencionan los ligandos en orden alfabético:
los ligandos aniónicos se citan como tales (H-, hidruro; HSO3-, hidrógenosulfito; ClO4-,
perclorato, etc..). Sin embargo, algunos tienen nombres algo modificado:
 Coordination Chemistry
Nomenclature

Forma de nombrar los ligandos:

Los ligandos aniónicos terminan en “o”.

Ejemplos: Cl- (cloro), SCN- (tiocianato), SO42- (sulfato), OH- (hidroxo), CN-
(ciano), NH2– (amido), O22- (peroxo), etc.

Casos particulares:
El SCN- puede coordinar por el N (tiocianato-N) o por el S (tiocianato-S).
El NO2– puede coordinar por el N (nitro) o por el O (nitrito).

(NH4)3[Cr(NCS)6] → hexa(tiocianato-N) cromato(III) de amonio

(NH4)2[Pt(SCN)6] → hexa(tiocianato-S) platinato(IV) de amonio.

Para los ligandos neutros los nombres no son sistemáticos.

Ejemplos: H2O (acuo), NH3 (amino), CO (carbonilo), NO (nitrosilo), etc
 Coordination Chemistry
Nomenclature

1. Si los compuestos son sales se nombra primero anión y después el catión. Así
en [Co(NH3)5Cl]Cl2 primero se da el nombre del Cl- y después [Co(NH3)5Cl]2+.

2. En los complejos, iones o moléculas los ligandos se nombran antes que el metal y
son mencionados en orden alfabético.

3. El número de ligandos iguales se menciona con prefijos (mono, di tri, tetra….)(bis-,

tris-, tetrakis-, ….). Los prefijos no se consideran parte del nombre que hay que
considerar en el orden alfabético.

4. Los nombres de los ligandos aniónicos acaban en la letra o, mientras que los
ligandos neutros usan su nombre ordinario. Algunos ligandos ordinarios tienen sus
propios nombres; H2O (acuo), NH3 (amino).

5. Al final se nombra el metal con la valencia entre paréntesis.

6. Si el compuesto es aniónico el nombre finaliza en ato

 Coordination Chemistry

Así, en el ión [CoCl(NH3)5]2+ ,se nombra primero el amoniaco después

el cloruro a continuación el cobalto y al final la valencia entre
paréntesis.

Pentaaminoclorocobalto (III)
 Coordination Chemistry
Excercise

1. ¿Cuál es el número de oxidación del metal central en [CoCl(NH3)5](NO3)2?

2. ¿Cuál es la carga del complejo formado por un ion metálico de platino(IV) rodeado por tres
moléculas de amoniaco y tres iones bromuro?.

3. Dado que un ion complejo contiene un cromo(III) enlazado a cuatro moléculas de agua y a
dos iones cloruro, escriba la fórmula.

4. [Pt(NH3)4]Cl2
5. cloruro de tetramin platino(II)

6. [Pt Cl2(NH3)2]
7. cis ó trans diamino dicloro platino(II)

8. K2[PtCl4]
9. tetracloro platinato(I)I de potasio
 Coordination Chemistry
Nomenclature

[Pt(NH3)4Cl2] [PtCl4]

IUPAC: Tetraaminedichloroplatinum(IV) tetrachloroplatinate(II)

 Coordination Chemistry
Isomerism in d-block metal complexes

Fac- and mer-isomers

Trans- and cis-isomers

[Pt(NH3)4Cl2] [PtCl4]

Classification of types of isomerism in metal complexes

 Coordination Chemistry
Structural isomerism: ionization isomers
Ionization isomers result from the interchange of an anionic ligand within
the first coordination sphere with an anion outside the coordination sphere

Examples of ionization isomers are [Co(NH3)5Br][SO4] and [Co(NH3)5(SO4)]Br

 Coordination Chemistry
Structural isomerism: ionization isomers
Ionization isomers result from the interchange of an anionic ligand within
the first coordination sphere with an anion outside the coordination sphere

Examples of ionization isomers are [Co(NH3)5Br][SO4] and [Co(NH3)5(SO4)]Br

 Coordination Chemistry
Structural isomerism: ionization isomers
Ionization isomers result from the interchange of an anionic ligand within
the first coordination sphere with an anion outside the coordination sphere

Examples of ionization isomers are [Co(NH3)5Br][SO4] and [Co(NH3)5(SO4)]Br

[SO4]2- free ion [SO4]2- bonded ion

Td point group Lowered symmetry
IR spectroscopy
1104 cm-1 (stretch) 1040 cm-1 (stretch)
613 cm-1 (deformation) 1120 cm-1 (stretch)
970 cm-1 (stretch)

These isomers can be readily distinguished by appropriate

qualitative tests for ionic sulfate or bromide
 Coordination Chemistry
Structural isomerism: hydration isomers
Hydration isomers result from the interchange of H2O and another ligand
between the first coordination sphere and the ligands outside it

Green crystals of chromium(III) chloride formed from a hot solution

obtained by reducing chromium(VI) oxide with concentrated hydrochloric
acid are [CrCl2(OH2)4]Cl⋅2H2O. When this is dissolved in water, the
chloride ions in the complex are slowly replaced by water to give blue-
green [CrCl(OH2)5]Cl2⋅H2O and finally violet CrCl3⋅6H2O.

The complexes can be distinguished by precipitation of

the free chloride ion using aqueous silver nitrate
 Coordination Chemistry
Structural isomerism: coordination isomers
Coordination isomers are possible only for salts in which both cation and
anion are complex ions; the isomers arise from interchange of ligands
between the two metal centres
 Coordination Chemistry
Structural isomerism: linkage isomers
Linkage isomers may arise when one or more of the ligands can
coordinate to the metal ion in more than one way, e.g. in [SCN]-, both the
N and S atoms are potential donor sites. Such a ligand is ambidentate

1065 and 1470cm-1 1310 and 1430 cm-1

The complexes can be distinguished using IR spectroscopy

 Coordination Chemistry
Structural isomerism: linkage isomers
The DMSO ligand can coordinate to metal ions through either the S- or
O-donor atom

An example of the interconversion of

linkage isomers involving the DMSO
ligand is shown in scheme; the
isomerization also involves a trans–cis
rearrangement of chloro-ligands
1055 cm-1

S-bonded DMSO O-bonded DMSO

υSO = 1080–1150 cm-1 υSO = 890–950 cm-1
 Coordination Chemistry
Class Work
What types of isomerism are possible for complexes with the following
molecular formulas: (a) [Pt(PEt3)3SCN]+, (b) CoBr(NH3)5SO4, (c) FeCl2⋅6H2O?
 Coordination Chemistry
Class Work
What types of isomerism are possible for complexes with the following
molecular formulas: (a) [Pt(PEt3)3SCN], (b) CoBr(NH3)5SO4, (c) FeCl2⋅6H2O?

(a)The complex contains the ambidentate thiocyanate ligand, SCN,

which can bind through either the S or the N atom to give rise to
two linkage isomers: [Pt(SCN)(PEt3)3] and [Pt(NCS)(PEt3)3].
(b)With an octahedral geometry and five coordinated ammonia
ligands, it is possible to have two ionization isomers:
[Co(NH3)5SO4]Br and [CoBr(NH3)5]SO4.
(c) Hydrate isomerism occurs as complexes of formula [Fe(OH2)6]Cl2,
[FeCl(OH2)5]Cl⋅H2O, and [FeCl2(OH2)4]⋅2H2O are possible
 Coordination Chemistry
Stereoisomerism: diastereoisomers
Distinguishing between cis- and trans-isomers of a square planar complex
or between mer- and fac-isomers of an octahedral complex is most
unambiguously confirmed by structural determinations using single-crystal
X-ray diffraction. Vibrational spectroscopy may also be of assistance.

IR active vibrations are

those associated with a
change in molecular
dipole moment
 Coordination Chemistry
Stereoisomerism: Square Planar Complexes
Werner studied a series of four-coordinate Pt(II) complexes formed by the
reactions of PtCl2 with NH3 and HCl. For a complex of formula MX2L2,
only one isomer is expected if the species is tetrahedral, but two isomers
are expected if the species is square planar.

Point group C2v Point group D2h

Platinum complexes are used in cancer chemotherapy, and it is found that only cis-
Pt(II) complexes can bind to the bases of DNA for long enough to be effective
 Coordination Chemistry
Class Work
Use the reactions indicated in the figure bellow to show how the cis and
trans geometries of a pair of platinum complexes may be assigned.

The preparation of cis- and trans-diamminedichloridoplatinum(II) and a chemical

method for distinguishing the isomers
 Coordination Chemistry
Class Work
The two square-planar isomers of [PtBrCl(PR3)2] (where PR3 is a
trialkylphosphine) have different 31P-NMR spectra. For the sake of this
exercise, we ignore coupling to 195Pt (I = 1/2 at 33 per cent abundance).
One isomer (A) shows a single 31P resonance; the other (B) shows two 31P
resonances, each of which is split into a doublet by the second 31P
nucleus. Which isomer is cis and which is trans?

Idealized 31P-NMR
spectra of two isomers
of [PtBrCl(PR3)2]. The
fine structure due to
Pt is not shown
 Coordination Chemistry
Stereoisomerism: Square Planar Complexes
In general, we can distinguish the isomers in a square planar complex
depending on the ligands as follow:

[MA2B2]

[MA2BC]
 Coordination Chemistry
Stereoisomerism: Square Planar Complexes
In general, we can distinguish the isomers in a square planar complex
depending on the ligands as follow:

[MABCD]

[MABCD]
 Coordination Chemistry
Stereoisomerism: Square Planar Complexes
In general, we can distinguish the isomers in a square planar complex
depending on the ligands as follow:

[M(AB)2]
 Coordination Chemistry
Stereoisomerism: Tetrahedral Complexes
The only isomers of tetrahedral complexes normally encountered are
those where either all four ligands are different or where there are two
unsymmetrical bidentate chelating ligands

[MABCD]

[M(AB)2]
 Coordination Chemistry
Stereoisomerism: Tetrahedral Complexes
The existence of a pair of chiral complexes that are each other’s mirror
image (like a right hand and a left hand), and that have lifetimes that are
long enough for them to be separable, is called optical isomerism

One enantiomer rotates the plane of polarized light in one direction and the
other rotates it through an equal angle in the opposite direction
 Coordination Chemistry
Stereoisomerism: Trigonal-bipyramidal and square-pyramidal
Complexes

Five-coordinate complexes are not stereochemically rigid; two chemically

distinct coordination sites exist within both trigonal-bipyramidal and
square-pyramidal complexes

[Ni(CN)5]3- can exist as both square-pyramidal and trigonal-

bipyramidal conformations in the same crystal
 Coordination Chemistry
Stereoisomerism: Trigonal-bipyramidal and square-pyramidal
Complexes

In solution, trigonal-bipyramidal complexes with monodentate ligands are

often highly fluxional: the conversion from one stereochemistry to another
may occur by a Berry pseudorotation

A Berry pseudorotation in which (a) a trigonal-bipyramidal Fe(CO)5 complex

distorts into (b) a square-pyramidal isomer and then (c) becomes trigonal
bipyramidal again, but with the two initially axial ligands now equatorial
 Coordination Chemistry
Stereoisomerism: Octahedral Complexes
Cis and trans isomers exist for octahedral complexes of formula [MA4B2],
and mer and fac isomers are possible for complexes of formula [MA3B3].
More complicated ligand sets lead to further isomers

There is only one way to accommodate the ligands in octahedral complexes of

general formula [MA6] and [MA5B]
 Coordination Chemistry
Stereoisomerism: Octahedral Complexes - cis and trans
isomers
Complexes in the [MA4B2] form may be placed on adjacent octahedral
positions to give a cis isomer or on diametrically opposite positions to
give a trans isomer

C2v D4h

Provided we treat the ligands as structureless points, the trans isomer has
D4h symmetry and the cis isomer has C2v symmetry
 Coordination Chemistry
Stereoisomerism: Octahedral Complexes - mer and fac
isomers
There are two ways of arranging the ligands in [MA3B3] complexes. In one
isomer, three A ligands lie in one plane and three B ligands lie in a
perpendicular plane (mer = meridional)

C2v C3v

In fac isomers, all three A (and B) ligands are adjacent and

occupy the corners of one triangular face of the octahedron
 Coordination Chemistry
Stereoisomerism: Octahedral Complexes - [MA2B2C2]

For a complex of composition [MA2B2C2], there are five different

geometrical isomers

C2h

All-trans isomer
 Coordination Chemistry
Stereoisomerism: Octahedral Complexes - [MA2B2C2]

For a complex of composition [MA2B2C2], there are five different

geometrical isomers

C2h

Three different isomers where one pair of ligands are trans

with the other two cis
 Coordination Chemistry
Stereoisomerism: Octahedral Complexes - [MA2B2C2]

For a complex of composition [MA2B2C2], there are five different

geometrical isomers

Enantiomeric pair of all-cis isomers

 Coordination Chemistry
Stereoisomerism: Octahedral Complexes - [MA2B2CD] and
[MA3B2C]
More complicated compositions, such as [MA2B2CD] or [MA3B2C], result in
more extensive geometrical isomerism

The rhodium compound [RhH(C≡CR)2(PMe3)3] exists as three

different isomers: fac, mer-trans, and mer-cis
 Coordination Chemistry
Stereoisomerism: Chirality and optical isomerism
A number of ligand arrangements at an octahedral centre give rise to
chiral compounds; isomers are designated Δ or Λ depending on their
configuration.

A very simple example is [Mn(acac)3], where three bidentate

acetylacetonato (acac) ligands result in the existence of enantiomers
 Coordination Chemistry
Stereoisomerism: Chirality and optical isomerism
As can be seen from the structures of the [CoCl2(en)2]+ isomers, the cis
isomer cannot be superimposed on its mirror image. It is therefore chiral
and hence optically active.

The trans isomer has a mirror plane and can be superimposed on

its mirror image; it is achiral and optically inactive
 Coordination Chemistry
Stereoisomerism: Chirality and optical isomerism
The absolute configuration of a chiral octahedral complex is described by
imagining a view along a threefold rotation axis of the regular octahedron
and noting the handedness of the helix formed by the ligands

Clockwise rotation of the helix is then designated !Δ (delta) whereas

the anticlockwise rotation is designated !Λ (lambda)
 Coordination Chemistry
Excercise
When the four-coordinate square-planar complex [IrCl(PMe3)3] reacts with
Cl2, two six-coordinate products of formula [IrCl3(PMe3)3] are formed. 31P-
NMR spectra indicate one P environment in one of these isomers and two
in the other. What isomers are possible?
 Coordination Chemistry
Excercise
When the four-coordinate square-planar complex [IrCl(PMe3)3] reacts with
Cl2, two six-coordinate products of formula [IrCl3(PMe3)3] are formed. 31P-
NMR spectra indicate one P environment in one of these isomers and two
in the other. What isomers are possible?
 Coordination Chemistry
Excercise
Which of the complexes (a) [Cr(edta)]-, (b) [Ru(en)3]2+, (c) [Pt(dien)Cl]+ are
chiral?
 Coordination Chemistry
Excercise
Which of the complexes (a) [Cr(edta)]-, (b) [Ru(en)3]2+, (c) [Pt(dien)Cl]+ are
chiral?
 Coordination Chemistry
Excercise
Which of the complexes (a) [Cr(edta)]-, (b) [Ru(en)3]2+, (c) [Pt(dien)Cl]+ are
chiral?
 Coordination Chemistry
Excercise
Which of the complexes (a) [Cr(edta)]-, (b) [Ru(en)3]2+, (c) [Pt(dien)Cl]+ are
chiral?
 Coordination Chemistry
Excercise
The diagrams below represent two tetrahedral, bis-chelate complexes.
Explain in terms of symmetry elements why A is achiral, but B is chiral.
Draw the structure of the other enantiomer of B
 Coordination Chemistry
Stereoisomerism: Chirality and optical isomerism
Chirality is not usually associated with square planar complexes but there
are some special cases where chirality is introduced as a result of, for
example, steric interactions between two ligands

Twist = the torsion angle A–B–C–D

Steric repulsions between the two R groups may cause the

aromatic substituents to twist so that the plane of each C6-ring
is no longer orthogonal to the plane that defines the square
planar environment around M
 Coordination Chemistry
Stereoisomerism: Chirality and optical isomerism
Chirality is not usually associated with square planar complexes but there
are some special cases where chirality is introduced as a result of, for
example, steric interactions between two ligands

Is this molecule achiral or chiral?

 Coordination Chemistry
Stereoisomerism: Chirality and optical isomerism
Chirality is not usually associated with square planar complexes but there
are some special cases where chirality is introduced as a result of, for
example, steric interactions between two ligands
Torsion angle = 18.6º

Two views of the structure of trans-[PdCl2(2-Mepy)2] showing the

square planar environment of the Pd(II) centre and the mutual
twisting of the 2-methylpyridine ligands